S1

Supporting Information for

A Combined Kinetic and Computational Study of the Reactions of Transient Germylenes

with Oxiranes and Thiiranes in Solution.

Svetlana S. Kostina and William J. Leigh*

Figure S1. Plots of (a) kdecay vs. [Q] and (b) (ΔA0)0 / (ΔAres)Q vs. [Q] for GePh2 in deoxygenated hexanes containing varying concentrations of CHO (l) and PrS (¡) at 25 °C; the solid lines are the least squares analysis of the data to eq. 3 (a) or 4 (b). Absorbance-time profiles were recorded at 500 nm and corrected for the underlying contributions due to the formation of Ge2Ph4 by scaled subtraction of absorbance-time profiles recorded at 440nm, following the published procedure.

S3

Figure S2. (a) Transient absorption spectra recorded 0.00-0.32 µs (○), 5.76-6.40 µs (□) and 69.60-70.24 µs (•) after the laser pulse, by laser flash photolysis of a deoxygenated hexanes solution of 2 containing 10 mM CHO. (b) Transient absorption spectra recorded 0.32-0.96 µs (○), 9.12-9.92 µs (□) and 69.92-70.72 µs (•) after the laser pulse, by laser flash photolysis of a deoxygenated hexanes solution of 2 containing 5.0 mM PrS. The insets show transient decay traces recorded at 280 nm, 350 nm and 440 nm.

S4

Figure S3. (a) Plots of (a) kdecay vs. [Et2S] for GeMe2 (¡) and GePh2 (□) in deoxygenated hexanes at 25 °; the solid lines are the least squares analysis of the data to eq. 3. (b) Transient absorption spectra recorded 0.32-0.64 µs (○), 4.48-5.12 µs (□), and 101.4-103.0 µs (Δ) after the laser pulse, by laser photolysis of 1a in deoxygenated hexanes containing 5 mM Et2S; (c) Transient absorption spectra recorded 0.16-0.48 µs (○), 9.12-9.76 µs (□), and 69.9-70.7 µs (Δ) after the laser pulse, by laser photolysis of 2 in deoxygenated hexanes containing 4.5 mM Et2S. The insets in (b) and (c) show transient absorbance-time profiles recorded at selected wavelengths throughout the range studied.

S5

Figure S4. 500 MHz 1H NMR spectra of a deoxygenated C6D12 solution containing 1b (0.040 M), CHO (0.180 M) and Si2Me6 (0.01 M), (a) after 15 min photolysis and b) before photolysis with 254 nm light.

S6

Figure S5. Concentration vs. time plots for 254 nm irradiation of a deoxygenated solution of 1b (0.040 M) in C6D12 containing CHO (0.180 M) and Si2Me6 (0.01 M). The solid lines are the least squares fits of the data, the slopes of which are (in mM min-1) CHO (¡), -0.293 ± 0.021; 3 (□), 0. 331 ± 0. 003. The concentration of 1b could not be quantified accurately because of spectral interferences.

S7

Figure S6. 500 MHz 1H NMR spectra of a deoxygenated C6D12 solution containing 1a (0.040 M), PrS (0.165 M) and Si2Me6 (0.01 M), (a) after 15 min photolysis and b) before photolysis with 254 nm light. * - unreactive impurity

S7

Figure S7. Concentration vs. time plots for 254 nm irradiation of a deoxygenated solution of 1b (0.045 M) in C6D12 containing PrS (0.165 M) and Si2Me6 (0.01 M). The solid lines are the least squares fits of the data, the slopes of which are (in mM min-1)

S8

S2

PrS (l), -0.63 ± 0.09; 3 (□), 0.340 ± 0.005; propene (4, ¡), 0.103 ± 0.003. The concentration of 1b could not be determined accurately because of spectral interferences.

Figure S8. 600 MHz 1H NMR spectra of a deoxygenated solution of 1a (0.047 M) in C6D12 containing PrS (0.07 M) and Si2Me6 (0.012 M), a) after 15 min of photolysis and b) before photolysis.

S8

Figure S9. Concentration vs. time plots for 254 nm irradiation of a deoxygenated solution of 1a (0.047 M) in C6D12 containing PrS (0.07 M) and Si2Me6 (0.012 M). The solid lines are the least squares fits of the data, the slopes of which are (in mM min-1) PrS (l), -0.42 ± 0.39; 1a (■), -0.58 ± 0.09; 5 (□), 0.39 ± 0.01; propene (4, ¡), 0.108 ± 0.012.

S9

Figure S10. -0.2 – 1.2 ppm region of the 600MHz 1H NMR spectra of the solution of Fig. S8, (a) before photolysis, (b) after 15 min photolysis, and (c) after 15 min photolysis and spiked with (Me2GeS)3 (6). * - unreactive impurity.

S9

Figure S11. Mass spectra of the product mixture of Fig. S8, elution times from the GC are indicated above each spectrum.

S11

Figure S12. 500 MHz 1H NMR spectra of a deoxygenated C6D12 solution containing 2 (0.065 M), CHO (0.085 M) and Si2Me6 (0.005 M), (a) after 35 min photolysis and b) before photolysis with 254 nm light. * - impurity

S12

Figure S13. Concentration vs. time plots for 254 nm irradiation of a deoxygenated solution of 2 (0.065 M) in C6D12 containing CHO (0.085 M) and Si2Me6 (0.005 M). The solid lines are the least squares fits of the initial 5 points, the slopes of which are 2 (●), 0.61 ± 0.07, DMB (ο), 0.34 ± 0.03 mM min-1. The concentration of 2 could not be determined accurately because of spectral interferences.

S12

Figure S14. 500 MHz 1H NMR spectra of a deoxygenated C6D12 solution containing 2 (0.058 M), PrS (0.08 M) and Si2Me6 (0.005 M), (a) after 36 min photolysis and b) before photolysis with 254 nm light. * - impurity

S13

Figure S15. Concentration vs. time plots for 254 nm irradiation of a deoxygenated solution of 2 (0.058 M) in C6D12 containing PrS (0.08 M) and Si2Me6 (0.005 M). The solid lines are the least squares fits of the initial 4 points, the slopes of which are PrS (■), -0.6 ± 0.2; 2 (ο), 0.47 ± 0.06, DMB (□), 0.39 ± 0.01, propene (●), 0.15 ± 0.01 mM min-1. The concentration of 2 could not be determined accurately because of spectral interferences.

S13

Computational Studies S14

Dimethylgermylene RB3LYP/6-311+G(d,p) output S14

Oxirane RB3LYP/6-311+G(d,p) output S14

Thiirane RB3LYP/6-311+G(d,p) output S15

Dimethylgermylene-oxirane anti complex B3LYP/6-311+G(d,p) output S15

Dimethylgermylene-oxirane transition state UB3LYP/6-311+G(d,p) output S16

S3

Dimethylgermylene-oxirane biradical UB3LYP/6-311+G(d,p) output S16

Dimethylgermanone B3LYP/6-311+G(d,p) output S17

1,1-Dimethyl-germa-2-oxetane B3LYP/6-311+G(d,p) output S17

Ethylene B3LYP/6-311+G(d,p) output S18

Dimethylgermylene-thiirane anti complex B3LYP/6-311+G(d,p) output S18

Dimethylgermylene-thiirane transition state UB3LYP/6-311+G(d,p) output S19

Dimethylgermanethione B3LYP/6-311+G(d,p) output S19

S4

Figure S1. Plots of (a) kdecay vs. [Q] and (b) (ΔA0)0 / (ΔAres)Q vs. [Q] for GePh2 in deoxygenated

hexanes containing varying concentrations of CHO (l) and PrS (¡) at 25 °C; the solid lines are

the least squares analysis of the data to eq. 3 (a) or 4 (b). Absorbance-time profiles were recorded

at 500 nm and corrected for the underlying contributions due to the formation of Ge2Ph4 by scaled

subtraction of absorbance-time profiles recorded at 440nm, following the published procedure.

S5

Figure S2. (a) Transient absorption spectra recorded 0.00-0.32 µs (○) and 5.76-6.40 µs (□) after

the laser pulse, by laser photolysis of 2 in deoxygenated hexanes containing 0.01 M CHO; (b)

Transient absorption spectra recorded 0.16-0.22 µs (○) and 6.88-7.01 µs (□) after the laser pulse,

by laser photolysis of 2 in deoxygenated hexanes containing 0.005 M PrS. The insets show

transient decay traces recorded at 280 nm, 350 nm and 440 nm.

S6

0.0 0.2 0.4 0.6 0.80

5

10

[Et2S] / mM

k dec

ay /

106

s-1

GeMe2: kC = (1.7 ± 0.2) × 1010 M-1s-1

GePh2: kC = (8.3 ± 0.4) × 109 M-1s-1

a

300 400 500 6000.00

0.01

0.02

0.03

0.04

0.05

Wavelength (nm)

ΔA

c

0 20 40 60 80Time / µs

300 nm

440 nm

280 nm

300 400 500 6000.00

0.01

0.02

Wavelength (nm)Δ

A

b

0 20 40 60 80Time / µs

310 nm

370 nm

Figure S3. (a) Plots of (a) kdecay vs. [Et2S] for GeMe2 (¡) and GePh2 (□) in deoxygenated

hexanes at 25 °; the solid lines are the least squares analysis of the data to eq. 3. (b) Transient

absorption spectra recorded 0.32-0.64 µs (○), 4.48-5.12 µs (□), and 101.4-103.0 µs (Δ) after the

laser pulse, by laser photolysis of 1a in deoxygenated hexanes containing 5 mM Et2S; (c)

Transient absorption spectra recorded 0.16-0.48 µs (○), 9.12-9.76 µs (□), and 69.9-70.7 µs (Δ)

after the laser pulse, by laser photolysis of 2 in deoxygenated hexanes containing 4.5 mM Et2S.

The insets in (b) and (c) show transient absorbance-time profiles recorded at selected

wavelengths throughout the range studied.

S7

Figure S4. 500 MHz 1H NMR spectra of a deoxygenated C6D12 solution containing 1b (0.040

M), CHO (0.180 M) and Si2Me6 (0.01 M), (a) after 15 min photolysis and b) before photolysis

with 254 nm light.

S8

0 5 10 150

5

175

180

Time / min

Con

cent

ratio

n / m

M CHO

3

Figure S5. Concentration vs. time plots for

254 nm irradiation of a deoxygenated

solution of 1b (0.040 M) in C6D12 containing

CHO (0.180 M) and Si2Me6 (0.01 M). The

solid lines are the least squares fits of the

data, the slopes of which are (in mM min-1)

CHO (¡), -0.293 ± 0.021; 3 (□), 0. 331 ± 0.

003. The concentration of 1b could not be

quantified accurately because of spectral

interferences.

Figure S6. 500 MHz 1H NMR spectra of a deoxygenated C6D12 solution containing 1b (0.045

M), PrS (0.165 M) and Si2Me6 (0.01 M), (a) after 15 min photolysis and b) before photolysis

with 254 nm light. * - unreactive impurity

S9

Figure S7. Concentration vs. time plots for

254 nm irradiation of a deoxygenated

solution of 1b (0.045 M) in C6D12 containing

PrS (0.165 M) and Si2Me6 (0.01 M). The

solid lines are the least squares fits of the

data, the slopes of which are (in mM min-1)

PrS (l), -0.63 ± 0.09; 3 (□), 0.340 ± 0.005;

propene (4, ¡), 0.103 ± 0.003. The

concentration of 1b could not be determined

accurately because of spectral interferences.

Figure S8. 600 MHz 1H NMR spectra of a deoxygenated solution of 1a (0.047 M) in C6D12

containing PrS (0.07 M) and Si2Me6 (0.012 M), a) after 15 min of photolysis and b) before

photolysis.

S10

Figure S9. Concentration vs. time plots for

254 nm irradiation of a deoxygenated

solution of 1a (0.047 M) in C6D12 containing

PrS (0.07 M) and Si2Me6 (0.012 M). The

solid lines are the least squares fits of the

data, the slopes of which are (in mM min-1)

PrS (l), -0.42 ± 0.39; 1a (■), -0.58 ± 0.09; 5

(□), 0.39 ± 0.01; propene (4, ¡), 0.108 ±

0.012.

Figure S10. -0.2 – 1.2 ppm region of the

600MHz 1H NMR spectra of the solution

of Fig. S8, (a) before photolysis, (b) after

15 min photolysis, and (c) after 15 min

photolysis and spiked with (Me2GeS)3 (6).

* - unreactive impurity.

S11

Figure S11. Mass spectra of the product mixture of Fig. S8, elution times from the GC are

indicated above each spectrum.

S12

Figure S12. 500 MHz 1H NMR spectra of a deoxygenated C6D12 solution containing 2 (0.065

M), CHO (0.085 M) and Si2Me6 (0.005 M), (a) after 35 min photolysis and b) before photolysis

with 254 nm light. * - impurity

0 5 10 150.00

0.010.05

0.06

0.07

0.08

0.09

CHO

2

7

time / min

Con

cent

ratio

n / M

Figure S13. Concentration vs. time plots for

254 nm irradiation of a deoxygenated

solution of 2 (0.065 M) in C6D12 containing

CHO (0.085 M) and Si2Me6 (0.005 M). The

solid lines are the least squares fits of the

initial 5 points, the slopes of which are 2

(●), 0.61 ± 0.07, DMB (ο), 0.34 ± 0.03 mM

min-1. The concentration of 2 could not be

determined accurately because of spectral

interferences.

S13

Figure S14. 500 MHz 1H NMR spectra of a deoxygenated C6D12 solution containing 2 (0.058

M), PrS (0.08 M) and Si2Me6 (0.005 M), (a) after 36 min photolysis and b) before photolysis

with 254 nm light. * - impurity

0 5 10 150.00

0.010.05

0.06

0.07

0.08

time / min

Con

cent

ratio

n / M

2

PrS

74

Figure S15. Concentration vs. time plots for

254 nm irradiation of a deoxygenated

solution of 2 (0.058 M) in C6D12 containing

PrS (0.08 M) and Si2Me6 (0.005 M). The

solid lines are the least squares fits of the

initial 4 points, the slopes of which are PrS

(■), -0.6 ± 0.2; 2 (ο), 0.47 ± 0.06, DMB (□),

0.39 ± 0.01, propene (4, ●), 0.15 ± 0.01 mM

min-1. The concentration of 2 could not be

determined accurately because of spectral

interferences.

S14

Calculated structures and energies Dimethylgermylene B3LYP/6-311+G(d,p) output Zero-point correction= 0.069978 (Hartree/Particle) Thermal correction to Energy= 0.075885 Thermal correction to Enthalpy= 0.076829 Thermal correction to Gibbs Free Energy= 0.040332 Sum of electronic and zero-point Energies= -2156.764460 Sum of electronic and thermal Energies= -2156.758553 Sum of electronic and thermal Enthalpies= -2156.757608 Sum of electronic and thermal Free Energies= -2156.794105 Ge -0.00000400 -0.51867200 0.00000000 C -1.49619700 0.83219900 -0.00727700 H -1.30130000 1.65872900 -0.69849800 H -2.46474500 0.38347200 -0.23495000 H -1.55005600 1.26340900 1.00217900 C 1.49622100 0.83217800 0.00727900 H 1.30143200 1.65864600 0.69861700 H 2.46480600 0.38344300 0.23476100 H 1.54984200 1.26354300 -1.00212100 Oxirane B3LYP/6-311+G(d,p) output Zero-point correction= 0.057135 (Hartree/Particle) Thermal correction to Energy= 0.060296 Thermal correction to Enthalpy= 0.061240 Thermal correction to Gibbs Free Energy= 0.033047 Sum of electronic and zero-point Energies= -153.778906 Sum of electronic and thermal Energies= -153.775745 Sum of electronic and thermal Enthalpies= -153.774801 Sum of electronic and thermal Free Energies= -153.802993 C -0.73333300 -0.37353200 0.00001000 C 0.73375600 -0.37311300 0.00001500 O -0.00042400 0.85531300 -0.00002800 H -1.27036200 -0.59118300 -0.91954300 H -1.27036800 -0.59112200 0.91957400 H 1.27079500 -0.59019600 -0.91964800 H 1.27078800 -0.59013500 0.91969500

S15

Thiirane B3LYP/6-311+G(d,p) output Zero-point correction= 0.054814 (Hartree/Particle) Thermal correction to Energy= 0.058198 Thermal correction to Enthalpy= 0.059142 Thermal correction to Gibbs Free Energy= 0.029521 Sum of electronic and zero-point Energies= -476.778846 Sum of electronic and thermal Energies= -476.775462 Sum of electronic and thermal Enthalpies= -476.774518 Sum of electronic and thermal Free Energies= -476.804139 C 0.73986000 -0.80636400 0.00000000 C -0.73984200 -0.80629100 0.00000000 H 1.25429400 -1.07931400 0.91415300 H 1.25429400 -1.07931400 -0.91415300 H -1.25434800 -1.07931600 0.91410300 H -1.25434800 -1.07931600 -0.91410300 S 0.00000000 0.87457400 0.00000000 Dimethylgermylene-oxirane anti complex B3LYP/6-311+G(d,p) output Zero-point correction= 0.129660 (Hartree/Particle) Thermal correction to Energy= 0.139871 Thermal correction to Enthalpy= 0.140815 Thermal correction to Gibbs Free Energy= 0.092578 Sum of electronic and zero-point Energies= -2310.555637 Sum of electronic and thermal Energies= -2310.545426 Sum of electronic and thermal Enthalpies= -2310.544482 Sum of electronic and thermal Free Energies= -2310.592718 C -1.38091900 -1.51398900 0.65492400 C -1.38034600 1.51443900 0.65447000 H -0.97703300 -2.47980600 0.34060700 H -1.14299200 -1.34577900 1.70904000 H -2.47295600 -1.56735900 0.56067300 H -0.97672900 2.48013500 0.33943300 H -2.47244100 1.56765300 0.56070900 H -1.14195600 1.34687100 1.70858600 C 2.40305400 0.73244000 -0.02050300 C 2.40308500 -0.73248100 -0.02104000 O 1.30383300 -0.00026300 0.57270800 H 3.00172700 1.27604300 0.70173600 H 2.14118800 1.25830200 -0.93326500 H 3.00177200 -1.27657800 0.70081400 H 2.14118300 -1.25765600 -0.93418800 Ge -0.74380200 -0.00006800 -0.52946600

S16

Dimethylgermylene-oxirane transition state UB3LYP/6-311+G(d,p) output Zero-point correction= 0.127339 (Hartree/Particle) Thermal correction to Energy= 0.137144 Thermal correction to Enthalpy= 0.138088 Thermal correction to Gibbs Free Energy= 0.091758 Sum of electronic and zero-point Energies= -2310.531368 Sum of electronic and thermal Energies= -2310.521563 Sum of electronic and thermal Enthalpies= -2310.520619 Sum of electronic and thermal Free Energies= -2310.566949 C -1.59318300 -1.37195500 -0.68222300 H -1.50277900 -2.35057900 -0.20775100 H -1.09230900 -1.39621400 -1.65549300 H -2.65502200 -1.16142300 -0.84274600 C -0.81094900 1.63270500 -0.79810000 H -0.26564700 2.49414300 -0.40655200 H -1.85058800 1.93816700 -0.95253700 H -0.39482000 1.34851400 -1.77090700 O 1.08261700 -0.52556200 0.36676600 C 2.23489500 0.31638700 0.42876300 C 2.55167400 -0.37166300 -0.81832700 H 2.00595000 1.38090700 0.35931100 H 2.85745900 0.09347600 1.29536100 H 2.17388600 0.00824900 -1.75636100 H 3.06224000 -1.32327400 -0.80252700 Ge -0.79043500 0.06061500 0.46954400 Dimethylgermylene-oxirane biradical UB3LYP/6-311+G(d,p) output Zero-point correction= 0.127038 (Hartree/Particle) Thermal correction to Energy= 0.137740 Thermal correction to Enthalpy= 0.138684 Thermal correction to Gibbs Free Energy= 0.089667 Sum of electronic and zero-point Energies= -2310.549134 Sum of electronic and thermal Energies= -2310.538432 Sum of electronic and thermal Enthalpies= -2310.537488 Sum of electronic and thermal Free Energies= -2310.586506 C 0.74456300 1.85936200 0.38979700 H -0.00339900 2.48164200 -0.10265400 H 0.52567200 1.80640800 1.46044800 H 1.72714000 2.31364900 0.24645300 C 1.92672100 -1.17962600 0.71016200 H 1.85712900 -2.20258300 0.33989000 H 2.96403300 -0.84440300 0.65076700

S17

H 1.59454500 -1.15274700 1.75174200 O -0.88759500 -0.73748600 -0.10109600 C -2.11913700 -0.10703800 -0.49375600 C -3.01009400 -0.04045900 0.69118400 H -2.56791400 -0.70369300 -1.29402300 H -1.92768800 0.89799700 -0.89883600 H -3.80775200 -0.75798400 0.83740500 H -2.74760500 0.60582400 1.52065800 Ge 0.75732100 0.00819800 -0.35898100 Dimethylgermanone B3LYP/6-311+G(d,p) output Zero-point correction= 0.074829 (Hartree/Particle) Thermal correction to Energy= 0.081814 Thermal correction to Enthalpy= 0.082758 Thermal correction to Gibbs Free Energy= 0.042939 Sum of electronic and zero-point Energies= -2232.022395 Sum of electronic and thermal Energies= -2232.015411 Sum of electronic and thermal Enthalpies= -2232.014466 Sum of electronic and thermal Free Energies= -2232.054285 O 0.00000000 1.77804100 -0.00007000 C -1.64900100 -0.94230800 0.00005700 H -1.67688100 -1.58216500 0.88551800 H -2.50970900 -0.27489500 -0.00047800 H -1.67643600 -1.58307700 -0.88475500 C 1.64900100 -0.94230800 0.00005600 H 1.67688500 -1.58216000 0.88552000 H 1.67643300 -1.58308100 -0.88475200 H 2.50970900 -0.27489400 -0.00048600 Ge 0.00000000 0.12386400 -0.00002100 1,1-Dimethylgerma-2-oxetane B3LYP/6-311+G(d,p) output Zero-point correction= 0.131248 (Hartree/Particle) Thermal correction to Energy= 0.140339 Thermal correction to Enthalpy= 0.141283 Thermal correction to Gibbs Free Energy= 0.096933 Sum of electronic and zero-point Energies= -2310.627846 Sum of electronic and thermal Energies= -2310.618754 Sum of electronic and thermal Enthalpies= -2310.617810 Sum of electronic and thermal Free Energies= -2310.662161 C 1.42205800 -1.62443200 -0.02544900 H 0.78901100 -2.51207100 0.00963400 H 1.98918500 -1.63489400 -0.95932300

S18

H 2.12845400 -1.65647700 0.80804900 C 1.42127600 1.62494000 -0.02662200 H 0.78726000 2.51212700 0.00189600 H 2.12314800 1.66073300 0.81055900 H 1.99343100 1.63246400 -0.95743600 O -1.02006900 -0.00121300 -1.20613100 C -2.08802200 -0.00019400 -0.22539900 C -1.34569700 0.00064700 1.13779800 H -2.71594700 -0.88737700 -0.36225500 H -2.71549400 0.88711200 -0.36354700 H -1.51467500 -0.88813300 1.74651100 H -1.51466700 0.89013300 1.74548100 Ge 0.32353600 0.00001000 0.06273500 Ethylene B3LYP/6-311+G(d,p) output Zero-point correction= 0.050784 (Hartree/Particle) Thermal correction to Energy= 0.053826 Thermal correction to Enthalpy= 0.054770 Thermal correction to Gibbs Free Energy= 0.028605 Sum of electronic and zero-point Energies= -78.564729 Sum of electronic and thermal Energies= -78.561686 Sum of electronic and thermal Enthalpies= -78.560742 Sum of electronic and thermal Free Energies= -78.586908 C 0.00000000 -0.66441900 0.00000000 C 0.00000000 0.66441900 0.00000000 H 0.92273800 -1.23519800 0.00000000 H -0.92273800 -1.23519800 0.00000000 H -0.92273800 1.23519800 0.00000000 H 0.92273800 1.23519800 0.00000000 Dimethylgermylene-thiirane anti complex B3LYP/6-311+G(d,p) output Zero-point correction= 0.127485 (Hartree/Particle) Thermal correction to Energy= 0.137812 Thermal correction to Enthalpy= 0.138756 Thermal correction to Gibbs Free Energy= 0.090475 Sum of electronic and zero-point Energies= -2633.558632 Sum of electronic and thermal Energies= -2633.548305 Sum of electronic and thermal Enthalpies= -2633.547361 Sum of electronic and thermal Free Energies= -2633.595642 C 1.71079900 1.52535000 0.53363800 C 1.71082200 -1.52533800 0.53363600 H 1.22262100 2.47912200 0.31687300

S19

H 1.70506300 1.35394900 1.61375100 H 2.75725200 1.61425100 0.21718400 H 1.22265900 -2.47911700 0.31687000 H 2.75727700 -1.61422200 0.21718200 H 1.70508400 -1.35393700 1.61375000 C -2.45802800 -0.73683100 -0.38477200 C -2.45802400 0.73683900 -0.38475500 H -3.29764900 -1.26124500 0.05447200 H -1.94139300 -1.24543800 -1.19061800 H -3.29764200 1.26124800 0.05450100 H -1.94138700 1.24546200 -1.19059000 S -1.31212000 -0.00001300 0.86080200 Ge 0.90839500 0.00000000 -0.54945900 Dimethylgermylene-thiirane transition state RB3LYP/6-311+G(d,p) output Zero-point correction= 0.125536 (Hartree/Particle) Thermal correction to Energy= 0.136012 Thermal correction to Enthalpy= 0.136956 Thermal correction to Gibbs Free Energy= 0.087871 Sum of electronic and zero-point Energies= -2633.541799 Sum of electronic and thermal Energies= -2633.531323 Sum of electronic and thermal Enthalpies= -2633.530379 Sum of electronic and thermal Free Energies= -2633.579464 C 1.40404400 1.63606700 0.72322000 C 1.57766300 -1.50258100 0.86147500 H 0.98951500 2.52105200 0.23736900 H 0.97044000 1.53064800 1.72210100 H 2.48262500 1.78024200 0.83658600 H 1.24133500 -2.46253700 0.46652600 H 2.66645800 -1.53328700 0.96386800 H 1.14481500 -1.34525200 1.85342000 C -2.60243000 0.75160500 0.48575000 C -2.79359500 -0.62263500 0.66702300 H -3.25559700 1.31443300 -0.16812600 H -2.04822100 1.32834400 1.21470200 H -3.53031600 -1.16479400 0.09009100 H -2.31468800 -1.15033900 1.48000200 S -1.17007200 -0.13439200 -0.78324000 Ge 1.08939700 -0.00759300 -0.39342200 Dimethylgermanethione B3LYP/6-311+G(d,p) output Zero-point correction= 0.073744 (Hartree/Particle) Thermal correction to Energy= 0.080993 Thermal correction to Enthalpy= 0.081937 Thermal correction to Gibbs Free Energy= 0.040906

S20

Sum of electronic and zero-point Energies= -2555.034269 Sum of electronic and thermal Energies= -2555.027020 Sum of electronic and thermal Enthalpies= -2555.026076 Sum of electronic and thermal Free Energies= -2555.067108 C -1.27968800 1.62705700 0.00009700 H -1.92049800 1.63789900 0.88564500 H -0.63818100 2.50698500 -0.00038600 H -1.92133500 1.63749400 -0.88484700 C -1.27968800 -1.62705700 0.00009600 H -1.92049400 -1.63790200 0.88564700 H -1.92133900 -1.63749000 -0.88484500 H -0.63818100 -2.50698500 -0.00039300 Ge -0.17791600 0.00000000 -0.00000400 S 1.87560000 0.00000000 -0.00011600